Process of refining hydrocarbon oils with sulphonic acid salts



A. LACHMAN Original Filed May 8. 1929 Oct, 6, 1931.

PROCESS of' REFINING HYDRocARBoN oILs WITH suLPHoNIc ACID sALTs la* 4,4 .41)4 1,11- we@ lNvENToR ier/fue ic/WMM ATroRNEY Patented Oct. 6, 1931 y UNITED STATES PATENT OFFICE Aura-UR LACHMAN, or BERKELEY, CALIFORNIA, AssIGNoa 'ro mcHrIELD oIL con- :PANY or CALIFORNIA, or Los ANGELES, CALIFORNIA, A coBPoRA'rIoN or' DELA- WARE PROCESS F BEFINING HYDROCARBON OILS WITH SUIPHGNIC ACID SALTB Original application led )lay 8, 1929, Serial No. 361,512. Divided and this application led lay 8, 1929.

Serial No. 361,523.

This invention relates to a process of purifying and refining hydrocarbon oils obtained by distillation or cracking of mineral oils, such as lubricating oils, lamp oils, gasoline stocks or distillates derived from oil shale. This application is a division of Iny applica-y tion for process oi rclining hydrocarbon oils, executed April 20, 1929, Serial No. 361,513, tiled May 8, 1929, which consists o lo'a similar method or process for purifying and relining mineral oil products with soluble metal salts.

The process of refining hydrocarbon oils, as described in this application, is applicable to all mineral oil products derived by distillation or cracking operations, such a lubricating oils, lamp oil stocks, gasoline stocks, distillates derived from oil shale, etc., and is particularly adaptable to gasoline stocks obtained by cracking higher boiling hydrocarbon oils. For the purpose of simplifying the description, reference will be made to gasoline only.

Crude gasoline stocks obtained by distilling 23 or cracking petroleum oils consist of a mixture of saturated and unsaturated hydrocarbons together With sulphur compounds, nitrogen bases and other substances of an undeiined nature. These latter substances are readily oxidizable at ordinary temperatures and are usually responsible for the change of color which takes place when refined gasoline is stored. These oxidizable substances are removed with diiiiculty when gasoline stocks are treated by the methods now in common use. In order to show the nature of my inven/ tion, it is desirable to describe the method now in common use in oil refineries, and particularly that step of refining gasoline stocks which consists in deodorizing and stabilizing the same. Crude gasoline stocks obtained by distillation of crude petroleum oil 5 or by'cracking a higher boiling petroleum oil, are customarily treated with approxi- Inately from 1 per cent to as high as 8 per cent by weight Sulphuric-acid, the quantity of sulphuric acid depending upon the nature 50 of the gasoline stock to be treated and the product desired. ally consists in comming/ling the gasoline stock with the required amount of sulphuric acid necessary to obtain the desired extraction, either by the well-known batch or continuous treatment, after which the products oi the 'acid reaction are permitted to settle and then Withdraw from the treated gasoline stock. 'lhe acid treated gasoline stock is then neutralized by Washing with a Water solution of an alkali and tinally with Water. This treatment removes most of the impurities, but subsequent treatments ,are usually necessary to deodorize and remove or convert corrosive sulphur compounds into non-corrosive bodies. For this purpose, a Water solution of sodium plumbiteor sodium hypochlorite is usually employed to render the gasoline sweet7 to the doctor test.

lhe general objections to a treatment of this character are as follows:

(l) Gasoline purified by this method frequently becomes disoolored when stored for a period of time;

(2) Considerable quantities of sulphuric acid are required, which are difficult to recover; l

(3) As high as l() per cent of the valuable stable unsaturated hydrocarbons contained in the gasoline stock may be lost; and

(4) The treatment must frequently be followed by a deodorizing or sweetening process, such as that heretofore described.

Now, 1 have discovered that the sulphuric acid normally used to treat crude gasoline stocks may be reduced to a high extent, and in many cases may be entirely eliminated by the employment of a water solution of certain Inetallic salts, or mixtures of the same, which may be zinc, copper, cadmium, mercury, iron, chromium, manganese, aluminum, nickel or cobalt Water soluble salts, such as the chloride, bromide, iodide, sulphate, nitrate, and also any of the Water soluble salts of the above named metals or organic acids, such as the sulphonic acids of benzol, toluol and Xylol, or the sulphonic acids derived from the treatment ot' petroleum oils with sulphuric acid. i I

The process described briefiy consists in This acid treatment usupassing the hydrocarbon oil product such as gasoline stock while in avapor state, through or in contact with a hot concentrated water solution of any of the aforesaid metallic salts or mixtures thereof. The gasoline stock so treated is usually pure enough for immediate use, although it sometimes may contain small amounts of hydrogen sulphide7 which may be removed by washing with an alkaline solution of sodium or calcium hydroxide, or the carbonatos of sodium or potassium.

The hydrocarbon oil stock to be treated by my invention may or may not have 'had a preliminary treatment with sulphuric acid, or other agents to partly purify the same, or may be first partly purified by my invention and the puritications completed by methods known in the art, such as treatment with caustic alkali, sulphuric acid, etc. In case of gasoline stocks produced by cracking high sulphur bearing crude petroleum oils or residuums, it may be advantageous to treat such gasoline stocks with small amounts of sulphuric acid before the treatment with a concentrated water solution of any of the aforestated metallic salts, which may also be followed by treatment with an alkaline water solution of sodium, potassium or calcium h ydroxide, or the carbonates of sodium or potassium.

Although a solution of less concentration may be employed which may range from 50 or less to approximately 85 per cent, the strength of the water solution of the metallic salt or mixture of salts employed is preferably a substantially concentrated solution, and the temperature employed for the treatment is approximately 300 to 400 degrees F., which normally luctuates, depending upon the vaporizing temperature of the oil under treatment.

With the foregoing preliminary explanation, the preferred embodiment of my invention will now be more fully explained by reference to the accompanying drawing which is a diagrammatic View of one form of apparatus which may be employed for carryinfr out the objects of ythe present invention.

eferring to the drawing, 2 indicates a pipe leading to a source of crude gasoline vapors not shown, such as a fractionating tower employed to separate the lower boiling oils from the higher boiling oils. B indicates a tower of suitable height and diameter filled with resistant or contact material, such as lire brick, s iral tile or the like, indicated at 3, which orms numerous tortuous passages through the tower, although it is to be understood that the well-known bubble cap contact tower may be employed. Disposed above the tower or adjacent to the same, is a tank l2 containing a substantially concentrated water solution of a metallic salt or mixtures of the same, as heretofore enumerated, having a concentration of from resales 50 per cent or less to as high as approximately 85 per cent. This tank is connected to the top of the tower by means of a pipe 4l having a regulating valve 5. This pipe terminates over la spreader plate 6 and this plate evenly distributes the water solution ot the metallic salt or salts when the valve 5 is opened, over the brick work or Contact material.. 'Ihe water solution of the metallic salt or salts flows downward through this contact material and may finally be discharged through the bottom by a pipe 7, after which it is treated for recovery. The tower B is also`provided with a steam or water inlet pipe H, which intermittently or continuously supplies a predetermined amount of water or steam to the tower. The hot gasoline vapors from the pipe 2 enter the lower end of the tower B at a point f). The oil vapors pass up through the nu-l merous contact passages in the tbrick work and thereby come into intimate contact with the said water solution ot' metallic salt or salts flowing over the same. Although other temperatures may be employed, both the water solution of metallic salt or salts and oil vapors are generally maintained at a temperature of approximately 300 to 400 degrees F., and the oil vapors are discharged at the upper end of the tower through a4v pipe l() which is connected with a condenser l1 of suitable construction. The gasoline vapors passing through the contact tower 'B at the temperature specified, vaporize a certain amount of water from the water solu tion of metallic salts and the purpose of the steam or water inlet pipe 8 is that of continuously maintaining the solution at a cer tain water content so as to maintain the necessary iiuidity which is essential for good' contact between the rising gasoline vapor and the down-flowing water solution of metallic salt or salts. Preferably the concentration of the water solution of metallic salt or salts is maintained at its predetermined limits of concentration by a con tinuous introduction of water or water vapor. Otherwise solid metallic salt or salts and solid sludge impurities may plug the passages through which the gasoline vapors are being conducted.

lVhile not always necessary, it is benelcial that the water solution of-metallic salt or salts contain hydroxides or oxides of any of the metals, or mixtures thereof, heretofore enumerated, before being introduced into the system. This may be accomplished by agitating the water solution of the metallic salt or salts with any of the hydroxides or oxides of any of the enumerated metals. The optimum amount of the metal oxide or hydroxide ranges from about l/Q of l per cent to 3 per cent by weight of the water solution of metallic salt or salts. In explanation, when the oxides or hydroxides of any of the aforementioned metals or mixtures thereof are soluble in substantial amounts in the sulphonic acid salt or salts solution at the temperature and pressure employed, it is no doubt that the beneficial action will be enhanced, but even if no substantial solubility exists, useful effects can be obtained if the oxides and liydroxides are suspended in 'the sulphonic acid salt or salts solution.

' The .reaction tower B is kept ull of the water'solution of the metallic salt or salts containing metallic bydroxides or oxides of any of the enumerated metals or mixtures of the same, and a fresh supply of approximately l5 pounds of the said solution is admitted for each barrel of gasoline stock under treatment and a corresponding amount of the spent solution is withdrawn at the same time.

The amount of water vapor required to replace the vaporized water from the water solution of metallic salt or salts varies within wide limits, depending upon the concentration of the solution employed, the temperature at which the operation is carried out and the nature and amount of inert gases which may accompany the gasoline Vapor being treated. Approximately 5() to 100 pounds of water or Water vapor will usually he sufficient for each barrel of gasoline stock treated. By this treatment the major portion of the impurities contained b the gasoline stock is removed and carried out with the Water solution of metallic salt or salts as a sludge and the purified gasoline vapors, when condensed, are suitable for use as a refined gasoline stock of high purity.

While the process herein described is well adapted for carrying out the objects of the present invention, it is to be understood that various modifications and changes may be made without departing from the invention,

such for example as the use of centrifugal or other mechanical mixers or the employment of any of the well-known contact towers wherein a water solution of a metallic salt or mixtures of metallic salts, either organic or inorganic, heretofore enumerated, may be commingled with or brought into contact with a petroleum oil vapor at the reacting temperatures and the invention includes all such modifications and changes as come within the scope of the appended claims.

What I claim is:

1. A process of refining mineral oils, comprising, vaporizing a mineral oil, contacting the va orized mineral oil with a water solution o a sulphonie acid salt of zinc, and then condensing the vapor.

2. A process of refining mineral oils, comprising, vaporizing a mineral oil by the applieation of heat, contacting the'heated vaporized mineral oil with a substantially concentrated water solution of a sulphonic acid saltof zinc, and then condensing the vapor.

3. Aprocess of refining mineral oils, comprising, vaporizing a mineral oil, contacting the vaporized mineral oil with a water solution-of a mixture of sulphonic acid salts of zinc, and then condensing the vapor.

4. A process of refining mineral oils, cornprising, vaporizing a mineral oil by the application of heat, contacting the heated vapor-ized mineral oil with a heated water soluvtion of a sulphonic acid salt of zinc, and then condensingthe vapor.

5. A process of refining mineral oils, comprising, vaporizing a mineral oil by the application of heat, contacting the heated vaporized mineral oil with a heated water solution of a sulphonic acid salt of zinc, heated to a temperature of not less than the vaporizing temperature of the vaporized mineral oil under treatment, and then condensing the vapor.

(i. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor at temperatures of' approximately 300 to 4U() degrees F., contacting the heated vapors with a water solution of a sulphonic acid salt of Zinc maintained at a substantially similar temperature, and then condensing the vapor.

7. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor at temperatures of approximately 300 to 400 degrees 1"., passing the heated vapors through or in contact with a concentrated water solution of sulphonic acid salts of zinc maintained at a substantially similar temperature and having a concentration of approximately 50-85%, and then condensing the vapor.

8. A process of refining mineral oils,corn prising, heating a mineral oil to form a vapor, contacting the heated vapor with a water solution of s'ulphonic acid zinc-salts containing zinc hydroxide, and then condensing the vapor.

9. A process of refining mineral oils, com-` prising, heating a mineral oil to form a vapor, passing the heated vapor through and in contact with a water solution of a mixture of sulphonic'acid zine salts containing from 1/ of 1 per cent to 3 per cent by weight of zinc hydroxide, and then condensing the vapor.

10. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor, passing the heated vapor through and in oontact with a water solution of a sulphonic acid salt of zinc containing from 1A; of 1 per cent to 3 per cent by weight of zinc hydroxide and zinc oxide, and then condensing the vapor.

11. A process of refining mineral oils, comprising, heating a mineral oil to form a vapor, passing the heated vapor through and in rl so iuid condition by the addition oi Water during contact or" vapors and treating solution, and condensing the vapor after passing through the solution.

l2. A process of refining mineral oils, con1- prising, commingling the vapor of a mineral oil with a water solution of a sulphonic acid zinc salt, and then condensing the Vapor.

l. A process of refining mineral oils, comprisiug, heating a mineral oil to form a vapor, passing the heated vapor through and in contact with a water solution of a sulphonic acid zinc salt containing zinc hydroxide, maintaining the solution in a fiuid condition by the addition ot water during contact of vapors and treating solution, and condensing the vapor ai'ter passing through the solution.

14. A process of refining mineral oils, comprising, heating a mineral oil to forni a vapor, passing the heated vapor through and in con* tact Witha water solution of sulphonic acid metal salts of zinc containing from 1X2 of l per cent to 3 per cent by Weight ot' zinc hydroxide and Zinc oxide, maintaining the solution in a fluid condition by the addition oi water during contact oi vapors and treating solution and condensing the vapor after passing through the solution.

l5. A process of refining mineral oils, comprising, heating a mineral oil to 'form a vapor, passing the heated vapor through and in contact with a Water solution'of a miX- ture of sulphonic acid salts of zinc, maintaining 'the concentration of the solution within predetermined limits by the addition of water during contact of vapor and treating solution and condensing the vapor after passing through the solution.

16. A process or' refining mineral oils, comprising, heating a mineral oil to form a vapor, at temperatures of approximately 300 to 400 degrees F., passing the heated vapors through and in contact with a Water solution of a sulphonic acid zinc salt maintained at a similar temperature, and having a concentration of approximately .5U-85%, maintaining the concentration ofthe solution as specified by the continuous addition of Water during contact of vapors and treating solution, and then condensing the vapor after passing through the solution.

17. A process of refining mineral oils, comprising, vaporizing a mineral oil, contacting the Vaporized oil with a water solution of a sulphonic acid salt of zinc, intermittently introducing Water into the solution of sulphonic acid salt of zinc and continuously condensing vapors of the purified mineral oil separated from the products of reaction and solution of sulphonic acid salt of zinc.

18.` A process-of refining mineral oils, comprising heating a mineral oil to form a vapor,

passing the vapor through and in Contact with a Water solution of sulphonic acid salts Lezama of zinc containing zinc hydroxide, intermittently introducing Water into the solution of sulphonic acid salts of zinc containing zinc hydroxide and continuously condensing the vapors of the purified mineral oil separated from the products of reaction and solution of sulphonic acid salts of zinc containing -zinc 

